Resinous derivatives from cellulose and other substances and alcohols



Patented June 2, 1942 RESINOUS iisnrva'rrvss r toiu csLLULosn AND o'ruaa SUBSTANCES AND awonons Eduard Fi rber, New Haven, Coma, assizn or to- Polyxor Chemical (20., Ina, NewHaven, Com,

a corporatlon ot New Jersey a g e Drawing. Application apt-u 21,1939,

9 Claims.

invention "relates to certain resinous de (c1. zso-la well below the temperature jrivatives produced Irom, on the onejhandg celluloseand substances which commonly accoin- P ny-cellulosein nature (for example; pentosansl t and. on the other hand, analcohol.

Unless,

ra s,

such for ior use as coatings or varnish. By heating to,

heated above moder tely high temsay' to ab out 180 C. or over, these derivatives aresoluble inmany organicsolv ents,

example as alcohols and ketones alike acetone, and in this"soluble form are adapted higher temperatures, say to above 180 0., they a [produce similarlyinsoluble articles moldedfrom the a t c or become insoluble with respect to these solvents.

Coatings for examplecan be rendered so insoluble by heating to such higher temperature after V which renders the derivative insoluble; thatis to say. preferably I hold the temperature. of this mixture at about being applied to the surlaceflto be protected thereby, or'the transformation can be used to soluble Iorm er the derivative; "These erivatlves [are generally of a" rather 150 C. Further, since this temperature is above the boilir ig polntofthe chosen alcohol, I usually subject such a mixture; during the reaction,

to a pressure sufficient to raise the boiling point of the alcohol to above the chosen temperature but not high enough to prevent the vaporization of the water, saya pressure-oi about fifty pounds per square inch; that is to 588,1 heat the-mixture ina closed vessel'irom which the water vaporfis allowed to-escape at this pressure. This elevated pressure prevents excessive loss or the alcohol, The completion of the reaction is indicated by 'the"disappearance of the cellulose.

The resulting mass is the desired derivative] As before indicated; I prefer to use cellulose, a cellulose-containing material, a pentosan, or a pentosan-containing material, or a. mixture there-,

dark color. They possesscertainadvantages over i 3 other resinous materials; 1orei rample, they pos- {se'ss a generally unusually" highdegree of reose substances sistance to acids and alkaline liquids.

A which commonly are found with cellulose will react with an alcohol to form these resinfous derivatives, when substantially concenand the water v sulphuric acid-appears toyact as a catalyst and trated sulphuric acidfis present in small amounts, 'oi the reaction tisremoved; the

p rtly as asulphonatlngf example of my process for producin these resinous derivatives in soluble term; I may take one hundred partsby welght'ol cellulose or sufllcient cellulose-containing material topro-y vide one hundred parts ofchemically pure cellulose) thoroughly distribute through the cellulose four and one-halt parts by weight of substandivided stat parts by weight of-amyl orisoaniyl alcohol; and remove,

tiallyconcentrated (e.g. 95% to 100%) sulphuric acid as by spraying with thesefcomponents- 'one hundred and ten say substantially as rapidly asformed,

the waterwhich is a product of the reaction. An elevated temperaturehastensfthe reaction and I bringsitmore quickly to its conclusion; furthermore, the water or the reaction can be driven vof! as formed by holding the mixture at a temperatureabove the boiling point I rel heat the mixture to 'andhold it at e temperature as reaso I t ble tutrsmee this example assumes the produc "tionjfof thejiderivative in its quite soluble form) of water. PreI- orator the basic Also as beforet indicated, only every small raw material; 7

quantity of the sulphuric acid isjrequired; usually lessthaii jfive by weight to one hundred partsby weight or the (chemically pure) cellulose (and/or other basic raw material) are 1 sufllcient; usually time between two parts and ir p tour andone-half paltsd f the acid to that quantity of the base material (e. g. cellulose). Greater quantities of the acid can be used however,

base material byiweigh't, especially when the (e.

1 g cellulose-containing materialscontain mineral impurities.

The sulphur'icacid should be -thoroughly distributed throughout thecbasic raw material. Especially when very small quantities of acidare employed, this may be done by spray- 1 ingthe acid; in finely divided form, into and throughout this base material as in the exam-' 40 the acid a very finely throughout the cellulose, then mix tion of the alcohol a suflicient volume of such carrier notreact with the acid, at least to an inhibi tive degree; that does not effectively inhibit the main n reaction; and that does hot deleteriously affect the reaction product? materia1ly. Acetic acid'ls especially suitable for suchja carrier or :solvent sinceitwets suitable base material readily. Fine emulsions oi the acid-in liquids that do not dissolve the acid can be used such for to six parts to one hundred parts of the anon-aqueous carrier, and mixed or solvent is used to assist or produce the thorough distribution of the'acid desired. Sucha carrier shouldbe a material that does;

escape of the water if desired.

of from one-and-one-half to threegram-mole- 'cules of the alcoholic material to one grammolecule of the (chemically pure) cellulose and/or its accompanying substances; usually I use about two gram-molecules to such quantity of the basic raw material; greater quantities can be included in the mixture however, either to make up for wastage duringthe reaction, to procure'a final product in the form of a liquid .thinner'thanotherwise, or for some other purpose. It will be-understood of course (as indicated elsewhere herein) that in thus referring to the gram-molecular weights of the basic raw materials (the molecular structures of which are complex), I am referring, as customary, to

weights which are based on the simplest or empirical formulae-of those materials; thus for. ex-

ample, the gram-molecular weight of cellulose herein referred to is 162, and of pentosans is 132. Inthe event that a celluloseor pentosan-conmaterial also contains a substantial .amount'ofilignin, the lignin can be counted as cellulose in determining the quantity of the alco- As beforeindicated, I usually heat the mixture to hastenthe reaction, and also as a means of removing the water of the reaction as this water is formed. Where the derivative is desired in the readily .soluble form, the reaction is carried on at atemperaturebelow that at which the insoluble formlis produced, saybelow 200 C.; if

the relatively. insoluble form is desired initially, the reaction is carried on at a suiiiciently higher temperature, say at or above 200 C. Where, as before indicated, the alcohol has a boiling-point which is rather low with respect to the temperature desired to hasten the reaction (or toiremove the reaction water, or to produce the rela- :tively insoluble-derivative) an elevated pressure can. be used to preventtheloss, or anundue loss, of the alcohol, at the same time the pressure being maintained sufficiently low to permit the g In the event that the relatively insoluble reaction product is desired in the first instanceand the reaction is carried on at an adequately high temperature @to secure that result, say a temperature about; or above 180 C. or 200 C., phenol serves paraticularly well as the alcohol becauseits rather high boiling point permits the use of lower pres- ,7 sures.

4 To avoid odors in the finished derivative, such as may be dueto residues or uncombined alcohol or phenol for example, equivalent small amounts of an aldehyde can be added to the mass near the end '01- the reaction. For example, furfural orglucose can be used for this purpose. I

-Where the derivative-is produced initially in its V soluble form, itcan be transformedintoits relatively insoluble form thereafter by heating .to the molded from its soluble form, or after being applied as a coating as before pointed out.

The particular temperature at which the soluble form of resinous product is converted into the insoluble; depends somewhat generally speaking, on the particular kind of alcohol that is or has been used. This will be bornetin mind where particular temperatures are referred to above.

As before indica ed, the resinous derivatives of my process generally have a dark color and,

are highly resistant to the action of acids and,

in the insoluble form, alkaline liquids. They react with chlorine or with nitric acid and can be acetylated. Their electrical resistance is high.

I claim:

v 1. The method of producing a resinous derivative which consists in forming a mixture of at least one material selected from the group consisting of cellulose and pentosans, a relatively small quantity of sulphuric acid but a quantity thereof which in weight does not exceed about six percent of the weight of the material of said group, and an alcohol, there being at least about one-and-one-half gram molecules of alcohol to each gram molecule of the material of said group,

permitting the same to react, and removing water of therreaction substantially as formed to permit the reaction to continue until the material of said 'group has substantially disappeared. 1

2. The method of claim 1, characterized by the fact that said alcohol is an alcohol of more 'than three and less than nine carbons per molecule.

3. The method of producing a resinous derivative which consists in mixing. at least one material selected from the group consisting of cellulose and pentosans with a relatively substantial quantity of sulphuric acid but a quantity thereof which in weight, does not exceed'about six percent of the weight of the material of said group, thereafter mixing. th'erewithan alcohol in proportions of at least about one-and-one-half gram-molecules of alcoholto each gram-molecule of the material of said group, permitting the mixture to react, and removing water of the reaction substantially continuously as that water is'formed to permit the reaction to continue until the material'of said group has substantially disappeared.

4. The method of claim 3, characterized by the fact that the, quantity of sulphuric acid, by weight, is between about two and five percent of the weight of the material of said group,the alcohol is an alcohol of more than three and less than nine carbons per molecule, and the alcoholic proportions are between about one-andappropriate temperature, say somewhat above 7 200 C.., for example as an incident to or as a separate step in the manufacture of articles one-half andabout three gram-molecules of ai cohol to one gram-molecule jof thematerial of said group. 7

5. The methodof claim 1, characterized by the fact that heat is applied to the mass to maintain the temperature thereof above C. and the mass is maintained under a pressure sufliciently high to prevent substantial loss of the alcohol at the temperature of the mass but less than sufllcient to prevent the vaporization of the water at said temperature, the water being removed by permitting the escape of the water vapor produced. l 7

6. The method of claim 1, characterized by the fact that the water of the reaction is removed by applying heat tothe 'mixture' to hold the temperature of the mixture well above, the boiling point of the water at the pressure at which the reaction is carried on, whereby the water escapes in the form 0L vapor substantially as rapidly as formed.

7. The method 01' claim 3, characterized by the factthat the quantity of sulphuric acid, by

" weight, is 01 the order of from two percent to flve'percent oi the weight or the material of the said group, and by the fact that the water of i the reaction is removed by applying heat to the mixture to hold the temperature of the mixture well above the boiling point of the water at the pressure at which the reaction is carried on, whereby the water escapes in the form of vapor substantially as rapidly as formed.

8. The method 01 claim 1, characterized by the facts that at least the maior part or the material or said group is cellulose, the quantity 0! the sulphuric acid, by weightgis oi the order of from two percent to five percent or the weight oi the material oi! said group, and for each one hundred sixty-two parts by weight or the material oi! said group there is about, by weight, from one-and-one-half to three gram-molecules of the alcohol.

- 9. The method or claim 1, characterized by the facts that a large part of the material of said group is a pentosanic material, the quantity or the sulphuric acid, by weight, is 01 the order of from two percent to five percent of the weight of the material of said group, and for each one hundred thirty-two parts by weight of the ma- .terial of said group there is about, by weight, 15 from one-and-one-half to three gram-molecules of the alcohol.

. i EDUARD 1 -31mm. 

